Heterocyclic compounds containing ethylene double bonds and process for their manufacture

ABSTRACT

The present invention comprises a process for the manufacture of heterocyclic compounds containing ethylene double bonds. This process is characterized by reacting a compound of formula   IN WHICH R1 represents a heterocyclic ring system of aromatic character which (a) contains at least one 5-membered or 6membered heterocyclic ring with at least one ring nitrogen atom, (b) is free of hydrogen atoms which (1) are bonded to ring nitrogen atoms and (2) which are replaceable by alkali metal, and (c) is bonded to a ring member of R2 by means of a ring member or has two adjacent ring members in common with two adjacent ring members of R2, in which R2 denotes a carbocyclic ring system of aromatic character which contains 6 ring members, and which optionally is condensed with a further aromatic or hydroaromatic ring system, and in which (b) the methyl group shown in the formula is in a p-position to the bond to R1, is reacted with a Schiff base in the presence of a strongly basic alkali compound, with the reaction medium to be used being dimethylformamide, which is practically anhydrous, except in the case of the use of an alkali hydroxide as the strongly basic alkali compound, in which case the alkali hydroxide may have a water content of up to 25 percent. The products obtained according to this process are valuable fluorescent compounds and useful as optical brighteners.

United States Patent 1191 Siegrist et al.

[ 1 Apr. 3, 1973 [54] HETEROCYCLIC COMPOUNDS CONTAINING ETHYLENE DOUBLEBONDS AND PROCESS FOR THEIR MANUFACTURE [75] Inventors: Adolf EmilSiegrist, Basel; Peter Liechti, Binningen; Erwin Maeder, Aesch/Bl;Leonardo Guglielmetti, Birsfelden; Hans Rudolf Meyer; Kurt Weber, bothof Basel, all of Switzerland [63] Continuation of Ser. No. 588,318, Oct.21, 1966,

abandoned.

[30] Foreign Application Priority Data Oct. 28, 1965 Switzerland..14902l65 F, 260/762, 260/304, 260/307 D, 260/308 B [51] Int. Cl...C09b 23/00 [58] Field of Search ..260/240 CA, 240 D [56] ReferencesCited OTHER PUBLICATIONS Katayanagi, J. Pharm. Soc. Japan, Vol. 68,pages 232-234 (1948). Crippa et al., Chemical Abstracts Vol. 42, Cols.2973 162974 (19 48). M Crippa et al., Chemical Abstracts, Vol. 43, C01.2209 (1949).

Avramoff et al., J. Am. Chem. Soc., Vol. 78, pages 4090 to 4096 (1956).

Miyano et al., Chem. Pharm. Bull. Vol. 15, pages 511 to 514 (1967).

Primary Examiner-John D. Randolph Attorney-l-larry Goldsmith, Joseph G.Kolodny and Mario A. Monaco [57] ABSTRACT The present inventioncomprises a process for the manufacture of heterocyclic compoundscontaining ethylene double bonds. This process is characterized byreacting a compound of formula in which R represents a heterocyclic ringsystem of aromatic character which a?! contains at least one 5- memberedor 6-membere eterocychc ring with at least one ring nitrogen atom, (b)is free of hydrogen atoms which (1) are bonded to ring nitrogen atomsand (2) which are replaceable by alkali metal, and (c) is bonded to aring member of R, by means of a ring member or has two adjacent ringmembers in common with two adjacent ring members of R,, in which R,denotes a carbocyclic ring system of aromatic character which contains 6ring members, and which optionally is condensed with a further aromaticor hydroaromatic ring system, and in which (b) the methyl group shown inthe formula is in a p-position tothe bond to R is reacted with a Schiffbase in'the presence of a strongly basic alkali compound, with thereaction medium to be used being dimethylformamide, which is practicallyanhydrous, except in the case of the use of an alkali hydroxide as thestrongly basic alkali compound, in which case the alkali hydroxide mayhave a water content of up to 25 percent. The products obtainedaccording to this process are valuable fluorescent compounds and usefulas optical brighteners.

11 Claims, No Drawings with compounds of formula HETEROCYCLIC COMPOUNDSCONTAINING ETHYLENE DOUBLE BONDS AND PROCESS FOR THEIR MANUFACTURE Thisapplication is a continuation of Ser. No. 588,318, filed Oct. 21, 1966,now abandoned and refiled as streamline continuation S'er. No. 142,388on May 11, 1971, now allowed.

The present invention comprises a process for the manufacture ofheterocyclic compounds containing ethylene double bonds. This process ischaracterized by reacting a compound of formula in which R, represents aheterocyclic ring system of aromatic character which (a) contains atleast one 5- membered or 6-membered heterocyclic ring with at least onering nitrogen atom, (b) is free of hydrogen atoms which l) are bonded toring nitrogen atoms and (2) which are replaceable by alkali metal, and(c) is bonded to a ring member of R by means of a ring member or has twoadjacent ring members in common with two adjacent ring members of R inwhich R denotes a carbocyclic or heterocyclic ring system of aromaticcharacter which contains 6 ring members, and which optionally iscondensed with further aromatic or hydroaromatic ring systems, and inwhich (b) the methyl group shown in the formula is in a p-position tothe bond to R,, is reacted with a Schiff base in the presence of astrongly basic alkali compound, with the reaction medium to be usedbeing a strongly polar, neutral to basic, organic solvent which (1) isfree of atoms, especially hydrogen atoms, which are replaceable byalkali metal and (II) is practically anhydrous, except in the case ofthe use of an alkali hydroxide as the strongly basic alkali compound inwhich case the alkali hydroxide may have a water content of up to 25percent.

Within the framework of the present invention two main types ofreactions according to formula (1) are above all of importance, andthese may be circumscribed as follows:

I. The reaction of anils of aldehydes of aromatic character, in themanner described under formula (I),

-CHa

in which formula (a) G, B and D each denote a ring atom of a S-memberedor 6-membered ring system of aromatic character, with at least one ofthe symbols G, B and D representing a nitrogen atom, and where D mayinstead of nitrogen also denote a carbon atom and G as well as B mayrepresent carbon, nitrogen, oxygen or sulphur atoms in the arrangementof ring systems which are in themselves known, (b) E represents the ringmember supplementation to give a S-membered or 6-membered ring system ofaromatic character, containing carbon, nitrogen, oxygen or sulphur atomsin the arrangement of ring systems which are in themselves known, and inwhich (c) the rings which are formed conjointly .with the symbol E maycontain further substituents, which like the substituent X do notcontain any atoms which may be replaced by alkali, especially hydrogenatoms, and p represents the numbers O or 1 and q the numbers 0, 1, 2 or3.

The aforementioned substituents may be of any desired aliphatic,cycloaliphatic, araliphatic or aromatic nature or may representfunctional substituents (e.g. carboxylic acid ester groups and the like)as long as they fulfil the preceding condition. 2. A further importantapplication of the reaction category disclosed under formula (1)comprises the reaction of anils of aldehydes of aromatic character, inthe manner given under formula (1), with compounds of formula CHa (Xah

in which formula (a) G and B each denote a ring atom of a S-membered or6-membered ring system of aromatic character and may represent carbon,oxygen, sulphur or nitrogen atoms, but at least one of the symbols G orB represent a nitrogen atom, and these atoms are present in thearrangement of ring systems which are in themselves known, (b) E denotesthe ring member supplementation to form a S-membered or 6- membered ringsystem of aromatic character, containing carbon, nitrogen, oxygen orsulphur atoms in the arrangement of ring systems which are in themselvesknown, and in which (c) the ring formed together with the symbol B maycontain further substituents, which like the substituent X do notcontain any atoms replaceable by alkali, especially hydrogen atoms,and-q may denote the numbers 0, l, 2 or 3.

These substituents may again, as explained under formula (1a), be of anydesired aliphatic, cycloaliphatic, araliphatic or aromatic nature or mayrepresent functional substituents (e.g. carboxylic acid ester groups).

The reaction which has been discovered in the present process is basedin principle on a reaction of the methyl group of compounds of formulacategory (1) with the azomethine grouping of a Schiff base (for examplebenzalaniline) with elimination of the amine components, according tothe following scheme:

cyclic ring, having 5 to 6 ring members and containing ring nitrogenatoms, this ring in turn being bonded to R and in fact either (a) insuch a way that one ring atom of this heterocyclic ring is bonded to aring atom of R by means of one bond, or (b) that this heterocyclic ringhas two, in each case adjacent, ring atoms in common with R that is tosay that it forms a condensed ring system. The statement that the ringsystem R may consist of one or more rings, denotes that for example (a)R consists only of one heterocyclic ring having to 6 ring members andcontaining ring nitrogen atoms, or (b) a heterocyclic compound asdefined under (a) contains further carbocyclic rings (especially6-rings) condensed to it (preferably a benzene or naphthalene ring), or(c) a heterocyclic compound as defined under (a) contains furtheraromatic rings of carbocylic or heterocyclic nature bonded via a singlevalence (that is to say not condensed), or (d) a heterocyclic compoundas defined under (a) is condensed with further heterocyclic rings, inwhich case hetero-atoms may also be common to two rings, or (e)combinations of the abovementioned variants with one another.

One of the reagents to be used for the process of the invention, namelythe compound according to formula (1), is capable of very broadvariation within the framework of the definition given above.

The text which follows summarizes the basic types and some selectedclasses of compounds according to formula ('1 without thereby imposing alimitation to these formulas.

A. Compounds of formula in which R denotes a heterocyclic ring systemwhich contains a S-membered to 6-membered heterocyclic ring with twoadjacent ring members which are directly bonded to R and at least onenitrogen atom which is exclusively bonded into the ring, and R denotes abenzene ring condensed with the hetero-ring, with the two carbon atomswhich belong to both rings and with the carbon atom bonded to the HC-group being in the 1,2,4-position relative to one another. In thiscase the benzene residue R is with advantage monocyclic and theheterocyclic ring of the residue R is only condensed with R The lattermay however of course still contain monovalent substituents, e.g.hydrocarbon residues, which may, like benzene residues or diphenylresidues, also be cyclic. Here emphasis should be placed on thecompounds of formula (6) F'\ CH3 and especially on the benzoxazoles offormula -cm n' o in which R denotes a benzene residue or naphthaleneresidue, X a hydrogen atom, a chlorine atom, a

methoxygroup or a methyl group and R a S-membered heterocyclic ring witha nitrogen atom exclusively bonded into the ring, this ring beingcondensed with the benzene ring in the manner stated. As has beenstated, the benzene residue R may contain further substituents, e.g.those mentioned for X, or further singly bonded benzene residues. B.Compounds of formula Gilly-(3H3 in which R denotes a heterocyclic ringsystem which contains at least one S-membered to 6-membered heterocyclicring with a ring member which is directly bonded to R and a nitrogenatom which is exclusively bonded into the ring, and R represents abenzene residue or naphthalene residue bonded to R and to the H C-groupin the l,4-position. Here the ring system R preferably consists of aS-membered to 6-membered heterocyclic ring and a benzene or naphthalenering condensed with this ring, with the rings referred to again beingable to have further substituents, as may be the case for compounds offormula Q-CHa in which R" denotes a benzene or naphthalene ring,condensed with the triazole, oxazole or diazine ring in the mannerindicated by the valency lines, and Y denotes a hydrogen atom or abenzene residue.

C. Compounds of formula in which R, denotes a heterocyclic ring systemhaving at most two rings, which contains a S-membered to 6- memberedheterocyclic ring with two to three ring members singly and directlybonded to the methylbenzene residue and at least one nitrogen atomexclusively bonded into the ring, X represents a hydrogen atom, ahalogen atom, a methoxy group or a methyl group, and n is equal to 2 or3. R may for example be an oxdiazole, thiadiazole, quinazoline,pyrimidine or 1,3,5-triazine residue. As Examples there may here beemphasized the oxdiazole and thiadiazole compounds of formula Hacc C CHal lI in which Y denotes an oxygen or sulphur atom. D. Compounds offormula in which R' denotes, for example, a monocyclic benzene residueand X a hydrogen atom, a chlorine atom, a methoxy group or a methylgroup, especially triazines of formula 25 MW, ,W

WQ HaC I T H'TTJ'Ha (26) N N @st 40 (27) H, CH;

Q N Q Q 1 H, CH:

as "W 43) H p' b,H-ca

H H H3C \Ny -peHr-CHs Additionally, the following explanations apply tothe preceding formulas: I (1) Terminal phenyl residues may additionallycontain further substituents of the alkyl series (especially having 1 to4 carbon atoms), the halogen series (especially chlorine) or the alkoxyseries (especially those having 1 to 4 carbon atoms). (2) Phenylresidues on s-triazine rings may additionally contain methyl groups. (3)Amongst substitution products of compounds according to formula (19)there are also to be included the corresponding 6-phenyl-benzoxazoles aswell as the analogous l-naphthoxazoles and Z-naphthoxazoles. (4)

The symbol HaC denotes that either a hydrogen atom or a methyl group,but in the entire molecule at least one methyl group, should be present.(5) The significance (as in the corresponding Examples) of the symbols Yand Z is Y, -O- or S and Z =N-- or =CH-. (6) The symbol W 77-. CQHBdenotes that in this position there may be either a hydrogen atom or aphenyl group.

As may be seen from the preceding compilation, all p-methylphenylderivatives of nitrogen-containing heterocyclics of aromatic characterare in principle accessible to the reaction of the invention and,summarizing, the most important categories should again be pointed out,namely such derivatives of pyrrole, pyrazoles, triazoles (l,2,3-, 1,2,4-or 1,3,4), tetrazole, pyridine, pyrimidine, pyrazine, quinazoline,quinoxaline, quinolines, triazines (l,3,5-, l,2,4-, l,2,3-), oxdiazoles(1,2,4-, 1,3,4-), benzoxazoles and naphthoxazoles, (iso)oxazoles,imidazoles as well as the corresponding ring systems which are condensedwith benzene or naphthalene rings, where these have not already beennamed.

The Schiff base to be used as the second reagent in the present processmust, as will be obvious, be free of reactive methyl groups, for examplethose in the p-position to the azomethine grouping. Possible Schiffbases are, in turn, the (known) condensation products of aldehydes ofaromatic character with primary amines (of aliphatic, aromatic orheterocyclic nature), whose amino group is bonded to a tertiary carbonatom. Compounds of this type may accordingly be written as azomethinecompounds of formula (45) Ar-CH=NC (tertiary) s in which Ar denotes anaromatic residue. In this, either one or both of the components requiredfor the synthesis of the Schiff bases (aldehyde and amine) mayconattaches to Schiff bases of aromatic, aldehydes with.

anilines, that is to say aromatic aldehyde-anils. Such anils for examplecorrespond to the formula N=HC in which k and I may be identical ordifferent and denote hydrogen atoms, chlorine atoms or methoxy groupsand in which h represents chlorine or,

preferably, hydrogen. Adjacent k and I may together also form a -OCl-l-O- group. Another important variant of aromatic anils corresponds tothe formula in which h (as above) represents a hydrogen atom or chlorineand Ar denotes a naphthyl or diphenyl residue. As monoaldehydes suitablefor the synthesis of these Schiff bases there may bequoted for example:aldehydes of the benzene series such as benzaldehyde or its halogenatedanalogues, such as the monochloroanalogues and dichloro-analogues,alkoxybenzaldehydes such as p-methoxy-benzaldehyde, alkylatedbenzaldehydes, provided these do not, contain any pmethyl groups, suchas toluyl-aldehyde, xylyl-aldehyde and cumoyl-aldehyde,methylenedioxy-benzaldehyde (piperonal), 4-dimethylamino-benzaldehyde,,4- diethylamino-benzaldehyde,, and diphenyl aldehyde; aldehydes of thenaphthalene series such as aand B- naphthaldehyde, and heterocyclicaldehydes such as for example furfurol and thiophenaldehyde.

As suitable amines there may be named,,by way of example, the anilines,naphthylamines or, as. an

aliphatic representative, tert. butylamine.

Compounds of formula (1) are reacted with the aldehyde-anils in thepresence of a strongly polar, neutral to alkaline, organic solvent whichis free of atoms, especially hydrogen atoms, which are replaceable byalkali metals. Such solvents are especially represented by di-alkylatedacylamides, preferably those of the. type in which Alkyl denotes aloweralkyl group (contain ing 1 to 4 carbon atoms), especially a methylgroup, Acyl the residue of a low carboxylic acid (containing 1 to 4carbon atoms), especially formic acid or acetic acid, or of phosphoricacid, and w gives the basicity of the acid. As important examples ofsuch solvents there may be quoted dimethylformamide, diethylformamide,dimethylacetamide and hexamethyl-phosphoric acidtriamide. It is alsopossible to use solvent mixtures.

The reaction furthermore requires a strongly basic alkali compound. Bythe term strongly basic alkali compounds there are to be understood,within the framework of the present invention, such compounds of thealkali metals (l.main group of the periodic table of elements) includingammonium as have a basic strength of at least about that of lithiumhydroxide; Accordingly, they may be compounds of lithium, sodium,potassium, rubidium, caesium or ammonium of, for example, thealcoholate, hydroxide, amide, hydride, sulphide or'strongly basic ionexchanger types. Potassium compounds of composition I in which m denotesan integer of l to 6, such as for example potassium hydroxide orpotassium tertiary-butylate, are advantageously used (above all whenmild reaction conditions as regards reaction temperature appear to beindicated). In the case of alkali alcoholates and alkali amides (andhydrides) it is here necessary to work in a practically anhydrousmedium, whereas in the case of alkali hydroxides watercontents of up to25 percent (for example contents of water of crystallization) areadmissible. In the case of potassium hydroxide a water content of up toabout 10 percent has proved appropriate. As examples of other alkalicompounds which maybe used there may be quoted sodium methylate, sodiumhydroxide, sodium amide, lithium amide, lithium hydroxide, rubidiumhydroxide, caesium hydroxide and the like. Of course it is also possibleto workwith mixtures of 'such bases.

In accordance with the preceding explanations, an

embodiment of the present invention which is important in practiceconsists of reacting anils of aldehydes of the benzene and naphthaleneseries with compounds which correspond to the formula bered ring systemof aromatic character containing carbon, nitrogen, oxygen or sulphuratoms in the arrangement of ring systems which are in themselves known,and in which (c) the ring formed together with the symbol B may containfurther substituents which do not contain any atoms, particularlyhydrogen atoms, which are replaceable by alkali, this reaction beingcarried out in the presence of an alkali compound having a basicstrength of at least that of lithium hydroxide, preferably potassiumtertiary-butylate or potassium hydroxide, in a solvent which correspondsto the formula in which Alkyl denotes a low alkyl group, Acyl theresidue of a low aliphatic, carboxylic acid or of phosphoric acid and wthe basicity of the acid, preferably in dimethylformamide.

It is appropriate to react the compounds of formula (1) with thealdehyde-anils in equivalent amounts, so that no component is present insignificant excess. As regards the alkali compound, it is advantageousto use at least the equivalent amount, that is to say at least 1 mole,of a compound having, for example, a KO group, per mole ofaldehyde-anil. When using potassium hydroxide a 4-fold to 8-fold amountis preferably employed.

The reaction of the invention may generally be carried out attemperatures in the range of between about 10 and 150C. If alcoholatesare used as the potassium compound in the reaction, then the applicationof heat is generally not necessary. The procedure is, for example, thatthe aldehyde-aniline is added to the mixture of the compound of formula(1), the solvent and the potassium alcoholate, preferably with stirringand with exclusion of air, at a temperature of between and 30C,whereupon the reaction takes place of its own accord, with a slighttemperature rise. When using potassium hydroxide it is frequentlynecessary to work at higher temperatures. For example the reactionmixture is slowly warmed to 30100C and then kept at this temperature forsome time, for example one-half to 2 hours. The products may be workedup from the reaction mixture by usual methods which are in themselvesknown.

The compounds obtainable by the present process are in part knowncompounds. New compounds are, amongst others, the compounds of thefollowing composition:

in which R denotes a heterocyclic ring system which contains aS-membered to o-membered heterocyclic ring having two adjacent ringmembers directly bonded to R and at least one nitrogen atom exclusivelybonded into the ring, R denotes a benzene ring condensed with thehetero-ring, with the two carbon atoms belonging to both rings and thecarbon atom bonded to the CH= group being in the 1,2,4-position to oneanother, and R denotes an aromatic residue.

ll. Compounds of formula in which a represents hydrogen, halogen, themethyl group or the methoxy group, Z and/or Z denotes a ring member =CHor =N- and a represents a hydrogen atom, a phenyl residue or a residueof the series in which R denotes an organic residue bonded to thetriazine ring by means of a benzene ring, R a benzene residue bonded inthe 1,4-position to the triazine ring and the CH= group, and R anaromatic residue.

IV. Triazine derivatives of formula in which B represents a phenyl ordiphenyl residue and B represents hydrogen, a phenyl residue or an alkylgroup having 1 to 4 carbon atoms, and in which terminal phenyl residuesmay contain an alkyl group with I to 4 carbon atoms, halogen or amethoxy group. V. Pyridine derivatives of formula in which V V or V;,represent hydrogen, a styryl residue or a p-phenylstyryl residue, but inwhich at least one residue V differs from hydrogen. Vl. Pyrimidinederivatives of formula in which W denotes a phenyl, diphenyl, l-naphthylor 2-naphthyl residue.

VlLCompounds of for L in which A represents a hydrogen atom, a methylgroup or a halogen atom, [3, denotes a residue of the series phenyl,diphenyl, l-naphthyl or Z-naphthyl and [3 represents a residue of theseries phenyl, diphenyl, styryl, stilbenyl, p-phenyl-stilbenyl,l-naphthyl or 2- naphthyl, and where terminal phenyl or naphthyl groupsmay additionally contain 1 to 3 alkyl groups, 1 to 2 halogen atoms or analkoxy group. Vlll. Benzoxazole derivatives of formula in which Xrepresents hydrogen or a methyl group, A denotes a phenyl group, adiphenyl group or a lnaphthyl or Z-naphthyl group, and A representshydrogen, halogen, an alkyl group containing 1 to 4 carbon atoms, astyryl group or p-phenylstyryl group, and where terminal phenyl ornaphthyl groups may additionally contain 1 to 3 alkylgroups, 1 to 2halogen atoms or an alkoxy group.

IX. Compounds of formula in which b represents a hydrogen atom or amethyl group, 7 represents a p-isopropylphenyl, diphenyl, lnaphthyl or2-naphthyl residue, and 8 denotes a residue of the series N /Y2 Q N /C\N \N where (l) d represents hydrogen or phenyl, e and f representphenyl, stilbenyl, p-phenylstilbenyl or benzostilbenyl, and furthermoreY represents a bridge member O-, --NH or N(alkyl)-, where (ll) U denoteshydrogen, a styryl residue or a p-phenylstyryl residue, and where (Ill)terminal phenyl or naphthyl residues may contain l to 3 alkyl groups, 1to 2 halogen atoms or an alkoxy group.

X. Compounds of general formula in which the symbol Q represents abenztriazole, naphthotriazole, 2-benzoxazole, 2-naphthoxazole,benzdiazine, 2-oxazole, s-triazine, as-triazine, oxdiazole (optionallyaryl-substituted) or benzthiazole residue and X and X denote branchedalkyl groups, or one of the substituents X and X,, denotes a phenylgroup or two adjacent substituents X and X denote a condensed-oncarbocyclic ring.

Xl. Compounds of formula Ga g in which G denotes hydrogen, an alkylgroup having 1 to 4 carbon atoms, a phenyl group, a phenylalkyl groupwith l to 4 carbon atoms in the alkyl group, halogen or a sulphonamidegroup, G represents hydrogen or an alkyl group or may, together with anadjacent residue G and the benzene ring to which these G-residues areattached, form a naphthalene ring. g represents hydrogen or methyl and Jdenotes a p-isopropylphenyl, diphenyl, l-naphthyl or 2-naphthyl residue,where terminal phenyl or naphthyl residues may additionally contain 1 to3 alkyl groups, 1 to 2 halogen atoms or an alkoxy group.

Xlll. Compounds of formula in which M represents a l,2,4-oxdiazole,1,3,4-triazole, thiadiazole, s-triazine or bisbenzoxazole residue offormula and X and X denote hydrogen, halogen, alkyl (straight-chain orbranched) or alkoxy groups, or one of the substituents X and X denotes aphenyl group or two adjacent substituents of a condensed-on carbocyclicring, and r represents the numbers 1 or 2.

XIV. Compounds of formula in which one to two residues 6 represent astyryl or pphenylstyryl residue and the remaining 5 residues denotehydrogen atoms.

XVI. Compounds of formula in which T represents hydrogen or a phenylresidue and R represents hydrogen, a styryl residue or a pphenylstyrylresidue.

XVII. 1,2,4-Triazine compounds of formula in which n represents a styrylor p-phenylstyryl residue. XVIII. Benzthiazole compounds of formula inwhich K represents a diphenyl residue or a lnaphthyl or 2-naphthylresidue. XIX. Compounds of formula in which L denotes a diphenyl ornaphthyl residue and L hydrogen, a styryl residue or a p-phenylstyrylresidue.

XX. Compounds of formula Z t N in which M and M represent hydrogen orphe nyl and Z represents a bridge member =CI-I or =N. XXI. Compounds offormula in which P represents hydrogen, an alkyl group containing 1 to 6carbon atoms or a phenyl group and P represents hydrogen or a phenylgroup.

XXII. Compounds of formula U: in which U U and U denote a hydrogen atom,a styryl residue or a phenylstyryl residue and at least one symbol Udiffers from hydrogen. XXII. Compounds of formula in which W and Wdenote a hydrogen atom, a styryl group or a p-phenylstyryl group, but atleast one symbol W differs from hydrogen.

Compounds of formula or I e (387) whose terminal aromatic rings mayadditionally contain alkyl groups, halogen atoms or alkoxy groups.

In these formulas quoted under numbers I to XXIV possible alkyl groupsin principle also include long chain alkyl groups, but in practice it ismostly alkyl groups containing up to about 8 carbon atoms, preferably 1to 4 carbon atoms, and especially branched-chain alkyl groups, whichrequire consideration.

Though again in the case of alkoxy groups higher members, that is to saythose containing 4 or more carbon atoms, as well as polyalkyleneoxygroups, are possible, the predominant practical significance resides inalkoxy groups containing 1 to 4 carbon atoms. Amongst the halogensquoted, chlorine is of especial interest.

The new compounds of the formulas of the preced ing groups I to XXIV maybe used as intermediates, for

example for the manufacture of dyestuffs or phar-- maceuticals. It isalso possible subsequently to introduce acid groups conferring watersolubility into the new compounds, by methods which are in themselvesknown.

A large number of compounds of general formula (49), especially those offormulas (50), (51), (52), (363), and (371) may, as has further beenfound, be used as optical brighteners provided they do not contain anychromophoric groups.

From the point of view of use as optical brighteners for the most variedorganic materials in which optical brighteners are desirable, the typesof compound which are advantageously accessible by the above process mayalso be classified as follows:

a. Compounds of formula in which A denotes a phenyl, diphenylyl ornaphthyl residue, A denotes a phenyl, diphenylyl, naphthyl or stilbenylresidue, and X, represents hydrogen, alkyl or halogen.

b. Compounds of formula in which A, represents hydrogen, an alkyl grouphaving 1 to 18 carbon atoms, an aryl residue, especially a phenylresidue, an aralkyl residue (especially a phenyl- C, .,-alkyl residue)or a halogen atom and s denotes an integer from 1 to 3, preferably 1,and X, represents hydrogen, alkyl or halogen. 0. Compounds of formula inwhich A,, represents hydrogen, an alkyl group having 1 to 18 carbonatoms, an aryl residue, especially a phenyl residue, an aralkyl residueespecially a phenyl- C -alkyl residue or a halogen atom and 5 denotes aninteger from 1 to 3, preferably 1, and X represents hydrogen, alkyl orhalogen.

d. Compounds of formula in which A, represents the remainder of thebenzene or naphthalene ring, A, denotes a diphenylyl or naphthylresidue, X represents hydrogen, alkyl or halogen and r represents 1 or2.

e. Compounds of formula i AQQ UQlQ? r ssqf hem s Q Q Q A denotes aphenyl, diphenylyl or'naphthyl residue or a residue A and these quotedaromatic residues may additionally contain 1 to 2 substituents X havingvthe significance of hydrogen, alkyl or halogen, preferably in thephenylene nuclei described under A,,.

The categories of compounds emphasized above as regards their brightenereffect possess a more or less pronounced fluorescence in the dissolvedor finely divided state. They are suitable for optical brightening ofthe most diverse organic materials of natural or synthetic origin, or ofmaterials containing such organic substances for which opticalbrightening is relevant. As such materials there may for example bequoted the following group of organic materials, without the recitalwhich follows in any way being inteded to express any limitation in thisrespect:

1. Synthetic organic hight molecular materials such as (A)polymerization products based on organic compounds containing at leastone polymerizable carboncarbon double bond (homopolymcrs or copolymersas well as their post-treatment products such as cross-linking products,graft products or degradation products, polymer dilutions and the like),as examples of which there may be quoted: polymers based on a,B-unsaturated carboxylic acids (for example acrylic compounds), olefinehydrocarbons, vinyl and vinylidene compounds, halogenated hydrocarbons,unsaturated aldehydes and ketones, allyl compounds and the like;furthermore polymerization products such as are obtainable by ringopening (for example polyamides of the polycaprolactam type),furthermore formaldehyde polymers, or polymers which are obtainable bothby polyaddition and by polycondensation such as polythioethers,polyacetals and thioplastics. (B) Polycondensation products orprecondensates based on bifunctional or polyfunctional compounds withgroups capable of condensation, their homocondensation andcocondensation products as well as post-treatment products (for examplesaturated and unsaturated, unbranched or branched, polyesters),polyamides, maleate resins, their pre-condensates and products ofanalogous structure, polycarbonates, silicone resins and others;(C)polyaddition products such as polyurethanes (cross-linked anduncross-linked) or epoxide resins. ll. Semi-synthetic organic materialssuch as for example cellulose esters, nitrocellulose, cellulose ethers,regenerated cellulose or their post-treatment products, and caseinplastics.

III. Natural organic materials with animal or vegetable origin, forexample based on cellulose or on proteins such as wool, cotton, silk,leather, wood compositions in a finely divided form, natural resins, andfurthermore rubber, guttapercha, balata as well as their post-treatmentproducts and modification products.

The organic materials requiring consideration may be present in the mostdiverse processing states (raw materials, semi-finished goods orfinished goods) and states of aggregation. They may thus be present inthe form of the most diverse shaped articles, for example as sheets,profiles, injection mouldings, chips, granules, and foams; films, foils,lacquers, strips, coverings, impregnations and coatings 'or filaments,fibers, flocks, bristles and wires. The materials quoted may on theother hand also be present in an unshaped state in the most diversehomogeneous and inhomogeneous forms of distribution and states ofaggregation, for example as powders, solutions, emulsions, dispersions,sols, gels, putties, pastes, waxes, adhesives and trowellingcompositions and the like.

Fiber materials may for example be present as continuous filaments,staple fibers, flocks, hanks, yarns, threads, fiber fleeces, felts,waddings, flocked structures, woven textile fabrics or laminates,knitted fabrics as well as papers, cardboards or paper compositions andthe like.

When used as brighteners, these compounds may be added to the materialsquoted either before or during shaping. Thus for example they may beadded to the moulding composition in the manufacture of films or othermoulded articles, or they may be dissolved, dispersed or otherwisefinely divided in the spinning composition before spinning. The opticalbrighteners may also be added to the starting substances, reactionmixtures or intermediate products for the manufacture of fully syntheticor semi-synthetic organic materials, that is to say also before orduring the chemical reaction, for example in the case of apolycondensation, a polymerization or a polyaddition.

The new optical brighteners may of course also be employed in all caseswhere organic materials of the type indicated above are combined withinorganic materials in any form. They are distinguished by exceptionallygood heat stability, light fastness and resistance to migration.

The amount of the new optical brighteners to be used, relative to thematerial to be optically brightened, may vary within wide limits. Aclear and durable effect can already be achieved with very smallamounts, in some cases for example with amounts of 0.001 per cent byweight. However amounts of up to about 0.5 per cent by weight and moremay also be used. For most practical purposes amounts of between 0.01and 0.2 per cent by weight are preferably of interest.

The compounds serving as brighteners may for example also be employed asfollows: (a) mixed with dyestuffs or pigments or as an additive to dyebaths, printing, etching or reserve pastes. Further also for thepost-treatment of dyeings, prints or discharge prints; (b) mixed withso-called carriers, antioxidants, light protection agents, heatstabilizers, chemical bleaching agents or as an additive to bleachingbaths; (c) mixed with cross-linking agents, finishing materials such asstarch or synthetically produced finishes; (d) in combination withdetergents, where the detergent and the brightener may be separatelyadded to the wash baths to be used, or preferably detergents are usedwhich contain the brightener mixed into them; (e) in combination withpolymeric carriers (polymerization, polycondensation or polyadditionproducts), in which the brighteners are optionally introduced alongsideother substances in a dissolved or dispersed form, (f) as additives tothe most diverse industrial products in order to make these moremarketable or to avoid disadvantages in their usability, for example asan additive to glues, adhesives, paints and the like.

The compounds which have been emphasized as optical brighteners may alsobe used as scintillators for various photographic purposes, such as forelectrophotographic reproduction or for super-sensitization.

In the tables which follow later on, symbols have the followingsignificance:

Column I= formula number Column ll structural elements Column Ill crudeyield in Column IV recrystallization medium, with these being designatedby the numbers listed below: 1 water, 2 ethanol, 3 dioxane, 4dimethylformamide, 5 tetrachlorethylene, 6 chlorobenzene, 7o-dichlorobenzene, 8 trichlorobenzene, 9 toluene, 10 n-hexane, ll=xylene.

Column V color of the purified reaction of product, with the latterhaving been designated by the numbers listed below: 1 colorless, 2almost colorless, 3 pale green 4 light green, 5 pale yellow, 6 lightyellow, 7 yellow, 8 pale greenish yellow, 9 light greenish yellow, 10greenish yellow.

Column VI melting point (uncorrected) in C.

Column VlI elementary formula and analytical data (upper linecalculated, lower line found).

EXAMPLE 1 and 7.05 g of 4-methoxybenzal-aniline (C H N=HC-C H OCH arestirred into 200 ml of anhydrous dimethylformamide with exclusion ofair, and are all at once treated with l 1.2 g of potassiumtertiarybutylate. The color of the reaction mixture changes immediatelyfrom pale yellow to dark blue and the temperature rises in the course of10 minutes .by about 12C. The mixture is stirred for a further 15minutes without external warming, during which the temperature drops byabout 3C. Thereafter 400 ml of water are added dropwise at 5 to 15C andthe reaction product is filtered off and washed with water untilneutral.

The moist filter residue is now dissolved in 270 ml of dimethylformamidewith warming, treated with ml of 10 percent hydrochloric acid and aftera few minutes with 300 ml of water and cooled to about 10C. Afterfiltration, washing with water and methanol and subsequent drying about11.7 g, corresponding to 93 percent of theory, of the compound offormula are obtained in the form of a pale yellow powder of meltingpoint 206 to 207.5C. Recrystallizing this three times fromtetrachlorethylene with the aid of Fullers earth yields pale yellowglistening platelets of melting point 214 to 214.5C.

Analysis: C H ON (377.43). Calculated: C 79.55, H 5.07, N ll.l3;found: C79.80, H 5.11, N 11.24.

If instead of the 7.05 g of 4-methoxybenzalaniline 6.05 g ofbenzalaniline are used, then 10.4 g, corresponding to 90 percent oftheory, of the compound of formula are obtained in the form of abeige-yellow light-colored powder which melts at 171 to 171.5C. Afterthree recrystallizations from tetrachlorethylene with the aid of Fullersearth: pale' greenish yellow glistening platelets of melting point 173.5to 174C are obtained. Analysis: C H N (347.40). Calculated: C 82.97, H4.93, N 12.10; found: C 82.96, H 5.04, N 12.23.

EXAMPLE 2 7.1 g of 1-[6'-phenyl-benzoxazolyl-(2)] -4-methylbenzene offormula and 4.53 g of benzalaniline are stirred into ml of anhydrousdimethylformamide with exclusion of air and treated all at once with7.45 g of potassium tertiary-butylate. The color of the reactionsolution changes immediately from .yellow to reddish brown and thetemperature rises over the course of 4 minutes, for example from 20C to31C. The mixture is stirred for a further 10 minutes without externalwarming, during which the temperature falls by about 5C. Thereafter 350ml of water are added dropwise at 5 to 15C and the precipitated reactionproduct is filtered off and washed with water until neutral.

The moist filter residue is now dissolved in 250 ml of dimethylformamidewith warming, treated with 25 ml of 10 percent hydrochloric acid andafter a few minutes with 350 ml of water and cooled to about 10C. Afterfiltering, washing with water and methanol and subsequent drying about5.38 g, corresponding to 57.7 percent of theory, of4-[6'-phenyl-benzoxazolyl-(2')]- stilbene of formula are obtained in theform of a light yellow powder which melts at 245 to 247C. After threerecrystallizations from tetrachlorethylene with the aid of Fullers earthlight greenish yellow glistening platelets of melting point 250 to 251Care obtained.

Analysis: C H O N (403.46). Calculated: C 83.35, M 5.25, N 3.47; found:C 83.11, H 5.44, N 3.46.

, In a similar manner, 10.01 g of the compound of formula pound offormula After three recrystallizations from ethanol with the aid ofactivated charcoal colorless glistening platelets of melting point 194to 194.5C are obtained.

Analysis: C ,,H O N S (488.65). Calculated: C 71.28, H 6.60, N 5.73;found: C 71.01, H 6.65, N 5.73.

EXAMPLE 3 7.13 g of 2-dipheny1y1-(4')-6-methylbenzoxazo1e of formula and4.53 g of benzalaniline are stirred into 200 ml of anhydrousdimethylformamide with exclusion of air and treated all at once with7.45'g of potassium tertiary butylate. The color of the reactionsolution changes immediately from pale yellow to dark brown and thetemperature rises by 5 to C over the course of 4 minutes. The mixture isstirred for a further 35 minutes without external warming, during whichthe temperature falls by a few C. Thereafter 350 ml of water are addeddropwise at 5 to 15C and the precipitated reaction product is filteredoff and washed with water until neutral.

The moist filter residue is now dissolved in 200 ml of dimethylformamidewith warming, treated with 25 ml of 10 percent hydrochloric acid andafter one hour with 200 ml of water, and cooled to about 10C. Afterfiltering, washing with water and methanol and subsequent drying about6.3 g, corresponding to 67.5 percent of theory, of the compound offormula 11.1.1) ...O AsCH=OH listed in the Table which follows may beprepared in a similar manner, with the duration of the reaction beingextended to minutes.

11 I 4 4 III IV v I I VII An X0 A9 21ll15 N 112 11 11 77.0 2 1 140-110.5 (131.02 115.011 N 4.71 w (104.37 115.24 N 4.55

C25H23ON 113. 4 11 C113 77 3 2 1 111-1415 C 84.115 110.56 N 3110 0 31.7011 00s N 1.00

ccII1 (zsHmozN 114 00. 5 2, 3 0 232-232. 5 C 33.35 II 5.25 N 3.47 0 c11c 33.23 11 5.12 N 3.45

Cz2H1nO-2NCI 115 CI 51.4 5 5 10041105 C 73.03 4.40 N 3.87 -0 C113 C73.10 H 4.51 N 3.00

C27H111ON 110 11 -11 117 5 3 215-210 0 30st H 5.13 N 3.75 C 86.85 115.22 N 3.75

117 ei zi N 3 0 M/ C 30.72 N 0.30 N 3.21

1111 T i minim N 1 I 11 1". 5 1' 11 2110 2110.5 (1 101.17 11 5.10 3 2 \iI I 37.1114 11 5.111 N 3 15 \2. i 1 1mm 1 11 (111 3/2 1 1115. 5-1110(100.32 11 0.25 N 3.17 (I 30.27 11 0.22 N 3.53 --(l(lll:1

II I III Iv v VI VII As Xn Av 1 (:IIIlIZlON N331 2 b II T7 5 2l8-24l x71II 5.00

c 87.85 H 4.86 N 3.45

CzgllQiON 121 cII. 74.4 3/2 a 179. 5-1805 (1 86.70 II 5.46 N 3.62 086.511 ll 5.53 N3.63

H v v c Ii E N a 0 22 CH. 100 4 u II-25II5 saon .4 w 1 C 87.7!) II 5.48N 3.06

l l i l \13 0 128 ll. 7 .0 32 ll 2zs-22s.5 c 87.81 5. I Q3 1 8 (187.56II 5.44 N 3.30

' CnllzgON N 3 20 124 z 3/2 10 202.5-203 c 8".8-1 II 5. o

/ 2 cm 85 0 c 56.59 H 5.41 N 3.35

4 ir 3 3. -CH 66.4 2 5 200-201 C 79.71 4.7 l CI 3 c 79.95 II 4.61 N 3.40

62 1123021 126 C1I3 52.6 10 11 5 191.5-192 (83.43 115.55 N336 0 C1171 C83.35 H 5.81 N 3.29

EXAMPLE 4 Analysis: C H ON (413.49). Calculated: C 87.14, H 5.93 g ofl-[5,6'-climethyl-benzoxazolyl-(2')]-4- 8 i'i f g 3 3: b methylbenzeneofformula I e ow ng enzoxazo e erIva LVeS may e I prepared m a sImIlarmanner: (127) 0 precipitated reaction product is filtered off, washedwith water and methanol and dried. About 4.5 g, corresponding to 43.5percent of theory, of the compound of formula are obtained in the formof a brown powder. After chromatography in tetrachlorethylene onactivated aluminum oxide and recrystallization from dioxane/ethanollight greenish yellow fine needles of melting point 222 to 223C areobtained.

Yield: about 12.8 g, corresponding to 90.5 percent of theory. Greenishyellow fine needles from odichlorobenzene. Melting point: 296.5 to298.5C. Analysis: C H ON (565.68). Calculated: C 89.17, H 5.52,N2.48;found:C88.96,l-l 5.70,N 2.64.

Yield: 22 percent of theory. Light greenish yellow fine glisteningneedles from tetrachlorethylene. Melting point 260 to 260.5C

Analysis: C H ,ON (399.47). Calculated: C 87.19, H 5.30, N 3.51; found:C 87.04, H 5.32, N 3.71.

' EXAMPLE 5 14.8 g ofthe compound of formula and 9.6 g of benzalanilineare stirred into 200 ml of anhydrous dimethylformamide with exclusion ofair and treated all at once with 16.8 g of potassium tertiary butylate.The color of the reaction mixture changes immediately from pale yellowto dark green and the temperature rises by about 7C in the course of 15minutes. The mixture is stirred for a further 1% hours without externalwarming, during which the temperature falls by about C. Thereafter 300ml of water are added dropwise at to C and the reaction product isfiltered and washed with water until neutral.

The moist filter residue is now dissolved in 300 ml of dimethylformamidewith warming, treated with ml of 10 percent strength hydrochloric acidand after 50 minutes with 300 ml of water and cooled to about 10C. Afterfiltering, washing with water and methanol and subsequent drying about18.1 g, corresponding to 94.1 percent of theory, of the compound offormula are obtained in the form of a light yellow powder of meltingpoint 160 to 161C. After three recrystallizations fromdimethylformamide-water [10 1] with the aid of activated charcoal lightyellow fine needles of melting point 162.5 to 163C are obtained.

Analysis: C H N (384.46). Calculated C 87.47, H

5.24, N 7.29; found: C 87.24, H 5.28, N 7.48.

If instead of the 9.6 g of benzalaniline 10.6 g of 4-methoxybenzalaniline are used then 18.9 g, corresponding to 94.2 percentof theory, of the compound of formula are obtained in the form of yellowfine needles which melt at 163.5 to 165C. On recrystallizing three timesfrom tetrachlorethylene with the aid of Fullers earth, luminous yellowfelted small needles of melting point 167.5 to 168.5C are obtained.Analysis: C H ON (414.48). Calculated: C 84.03, H 5.35, N 6.76; found: C84.14, H 5.42, N 6.89.

Using 10.8 g of 4'-chlorobenzalaniline about 19.8 g, corresponding to94.5 percent of theory, of the compound of formula l c..=w m N areobtained. Yield: 94.5 percent of theory. Pale yellow very fine crystalsfrom dimethylformamide/ethanol. Melting point 185 to 186C.

Analysis: C H N Cl (418.93). Calculated: C 80.28, H 4.57, N 6.69; found:C 80.06, H 4.57, N 6.66:

EXAMPLE 6 6.65 g of the compound offormula are added dropwise at 10 to20C and the reaction product is filtered off and washed with water untilneutral.

The moist filter residue is now dissolved in 3 l of dimethylformamidewith warming, treated with 25 ml of 10 percent strength hydrochloricacid and after 1 hour with 3 l of water and cooled to about 10C. Afterfiltering, washing with water and methanol and subsequent drying about10.5 g, corresponding to 83.5 percent of theory, of2,5-bis-[4"-methoxystilbenyl-(4 )]-1 ,3,4-thiadiazole of formula areobtained in the form of a yellow powder of melting point 294 to 297C.Two recrystallizations from odichlorobenzene with the aid of Fullersearth yield light yellow glistening platelets of melting point 300 to300.5C.

Analysis: C ll O N S (502.64). Calculated: C 76.46, H 5.21, N 5.57;found: C 76.75, H 5.36, N 5.50.

If instead of the 6.65 g of 2,5-bis-[4'-methyl-phenyl-(l')]-l,3,4-thiadiazole of formula an equimolecular amount of2,5-bis-[4'-methyl-phenyl- (l)]-l ,3,4-0xdiazole of formula are usedthen about 10.8 g, corresponding to 89 percent of theory, of2,5-bis-[4"-methoxy-stilbenyl-(4')]- 1,3,4-oxdiazole of formula areobtained in the form ofa light yellow powder which after threerecrystallizations from o-dichlorobenzene with the aid of Fullers earthyields pale yellow glistening platelets of melting point 31 1 to 311,5C.Analysis: C H O N (486.54). Calculated: C 78.99, H 5.39, N 5.76; found:C 78.90, H 5.67, N 5.78.

1n a similar manner, 3-[4-methyl-phenyl-(1)]-5- phenyl-l ,2,4-oxdia zoleof formula and 3,5-di-[4'-methyl-phenyl-(1)] 1,2,4-oxdiazole of f la(no) ../.N\

ll 1 N may be used to produce the 1,2,4-oxdiazole derivatives of formulawhich are listed in the following Table.

are obtained in the form of a yellow powder of melting point 243.5 to246.5C. After chromatography in tetrachlorethylene on activated aluminumoxide and recrystallization from dioxane-ethanol, pale greenish yellowfelted small needles of melting point 235.5"C are obtained.

Analysis: C H ON (441,51). Calculatedi C 81.61, H 5.25, N 9.52; found: C81.70, H 5.38, N 9.45.

EXAMPLE 8 11.7 g of 2,4,6-tri-[4-methylphenyl (1)]-1,3,5- triazine of.formula I T 1v \1 WI 142 H n 1 2 159-1505 CzzHmONz C 81.46 H 4.97 N 8.64C 81.51 H 4.91 N 8.78

H3 11 5 1 228 228. 5 CzsHzoONr C 83.07 H 5.03 N 7.00 C 84.20 H 5.15 N6.77

144 H 8 246. 53-247 CaoHzzONz -CH=CI-1 C 84.48 5.20 N 6.57 C 84.61 H5.25 N 6.53

145 CH CH Q 1111 7 1 3211-330 0 CnHsnONz 1 87.17 H 5.23 N 4.84 C 87.14 H5 28 N 4.79

EXAMPLE 7 His) 5 C 0 C OH 10.8 g of 2,4-d1phenyl-6-[4'-methy1phenyl 1' ma N 1. g r m f V a (146) C Q eQ- and 18.1 g of benzalaniline are stirredinto 350 ml of anhydrous dimethylformamide with exclusion of air andtreated all at once with 28.0 g of potassium tertiary-butylate. Thecolorof the reaction mixture changes immediately from pale yellow to violetand the temperature rises over the course of 5 minutes by about 10C. Themixture is stirred for a further 1% hours without external warming,during which the temperature again drops. Thereafter 350 ml of water areadded dropwise at 10 to 20C and the reaction product is filtered off andwashed with water until neutral.

The moist filter residue is now dissolved in 500 ml of dimethylformamidewith warming, treated with 50 ml of percent strength hydrochloric acidand thereafter with 500 ml of water. The mixture is cooled to about 10C,filtered off, and the residue first washed with water, then withmethanol and dried. About 20.4 g, corresponding to 99.5 percent oftheory, of 2,4,6-tri- [stilbenyl-(4')]-l ,3,5 -triazine of formula new"OCH:

are obtained in the form of a yellow powder of melting point 263.5 to265C. After chromatography in odichlorobenzene on activated aluminumoxide and two recrystallizations from tetrachlorethylene yellow veryfine small needles of melting point 300C are obtained.

Analysis: C H O N (705.82). Calculated: C 81.68, H 5.57, N 5.95; found:C 81.53, H 5.51, N 5.87.

EXAMPLE 9 11.7 g of 2,4,6-tri-[4'-methylphenyl-(l')]-l,3,5- triazine offormula (148), 18.1 g of benzalaniline and 12.6 g of potassium hydroxidepowder containing about 10 percent water are stirred into 300 ml ofdimethylformamide with exclusion of air, in the course of which a darkblue color is produced after a few minutes. The temperature is raised toC over the course of 1 hour, and the mixture stirred for a further 40minutes at this temperature and then cooled to about 10C. Now ml ofwater, ml of 10 percent strength hydrochloric acid and a further 250 mlof water are successively added dropwise at 10 to 20C. The precipitatedreaction product is filtered off, washed with water until neutral andfreed of a byproduct by further washing with methanol. After dryingabout 19.7 g, corresponding to 96.2 percent of theory, of2,4,6-tri-[stilbenyl-(4')]-l,3,5-triazine of formula (149) are obtainedin the form of a yellow powder which melts at 262 to 267C. Afterchromatography in tetrachlorethylene on activated aluminum oxide andsubsequently three recrystallizations from tetrachlorethylene, lightgreenish yellow felted small needles of melting point 293 to 293.5C areobtained. Analysis: C H N (615.78). Calculated: C 87.77, H 5.40, N 6.82;found: C 87.55, H 5.55, N 6.98.

If instead of the 18.1 g of benzalaniline 25.73 g ofdiphenyl-(4)-aldehyde-anil are used and the reaction is carried out for30 minutes at 60C, then the 2,4,6-tri-[4"-phenyl-stilbenyl-(4)]-1,3,5-triazine of formula Yield: 94.0 percent oftheory. Light yellow very fine small needles from tetrachlorethylene.Melting point: 3l5to317C. V Analysis: C H N Cl (719.12 Calculated: C75116, H 4.21, N 5.84; found: C 75.17, H4-.2 2,N. 6.00. From2,4-diphenyl-6-[4-methylphenylr(1)]-l,3-,5-triazine of formula (146-)and diphenyl- (4.)-aldehyd-anil, the compound of formula v Yield: 98.5percent of theory. Light yellow very fine needles fromtetrachlorethylene. Melting point: 284 to 285C.

Analysis: C l-1 M (487.57). Calculated: C 86.21, H

5.17, N 8.62; found: C 86.35, H528, N--.854.

From 2,4,6-tri-[2',4-dimethyl-phenyl-(1')]-1,3,5- triazine of formula(154) l V I an v N H i HAG- and diphenyl-(4)-aldehydeanil, thecompoundof formula EXAMPLE 10 16.87 g of2,4-di-[4'-methylphen'yl-(1')]-6-phenyl- 1,3,5-triazine of formula 1 1 N/N C [Melting point: 218 to 218.5C], 18.1 g of benzalaniline and 50 g ofpotassium hydroxide powder containing about 10 percent water are stirredinto 400 ml of dimethylformamide with exclusion of air, duringwhich aviolet color is produced after a few minutes. The temperature is raisedto 60C over the course of 30 minutes, and the mixture stirred for afurther 30 minutes at this temperature and then cooled to roomtemperature; Now 50 ml of water and 500 ml of 10 percent strengthhydrochloric acid are successively added dropwise. The-precipitatedreaction product is filtered off, washed with water until neutral andfreed of a byproduct by further washingwith 300 ml of methanol. Afterdrying about 24.8 g, corresponding to 96.6 percent of theory, of2,4-di-[stilbenyl-(4')]-6-phenyl- 1,3,5-triazine of formula 1 N bllisted in the following Table may be produced in a similar manner.

Yield: 94.3 percent of theory. Light yellow felted fine small needlesfrom tetrachlorethylene. Melting point 226.5 to 227C. I

Analysis: C H N 2 (460.55). Calculated: C 88.66, H 5.25, N 6.08; found:C 88.46, H 4.96, N 6.04.

14.8 g of the compound of formula (131), 9.06 g of benzalaniline and gof potassium hydroxide powder containing about 10 percent water arestirred into 300 ml of dimethylformamide with exclusion of air, duringwhich a violet color gradually develops. The temperature is raised to60C over the course of minutes, and the mixture stirred for a further 30minutes at this temperature and then cooled to room temperature. Now 100ml of water and 260 ml of 10 percent strength hydrochloric acid aresuccessively added dropwise. The precipitated reaction product is washedwith a great deal of water and thereafter with 600 ml of methanol and isdried. About 16.7 g, corresponding to 87.0 percent of theory, of thecompound of formula (132) are obtained in the form of a yellow powderwhich melts at 159.5 to 160C. After chromatography in tetrachlorethyleneon activated aluminum oxide and recrystallization from dioxane-ethanolpractically colorless felted fine small needles of melting point 164.5to 165C are obtained.

Analysis: C H N (384.46). Calculated: C 87.47, H 5.24, N 7.29; found: C87.20, H 5.10, N 7.32.

The following quinazoline derivatives may be prepared in a similarmanner.

1 B1 132 lll lv v vl V11 1 c 86.43 11 0.10 N 7.38 ':o1 t c 80.33 115.08N 7.55

1.60" 94. 3 5 8 1. .40. 5241 clr Ha Ng Q c 87.58 11 5.30 N 7.13 C 87.44H 5.55 N 7.13

101.. m H 01. 0 7 0 351-352. 5 0011mm C 88.39 5.30 N 0.31 c 88.33 H 5.43N 6.28

102.... out 08. 0 3/2 10 325-328 oeNflN3 0 88.18 11 5.00 N 5.82 m pCHt C88.37 11 6.28 N 5.80

M c 80.01 11 5.30 N 5.55 c 88.08 11 5.51 N 5.73

EXAMPLE 1 1 Yield: 93.5 percent of theory. Light yellow fine feltedsmall needles from point:l98 to 198.5C Analysis: C H N (384.46).Calculated: C 87.47, H 5.24, N 7.29; found: C 87.67, H 5.35, N 7.12.

tetrachlorethylene. Melting Yield: 96.5 percent of theory. Luminousgreenish yellow fine small needles from o-dichlorobenzene. Meltingpoint: 384 to 385C.

Analysis: C H N (638.77). Calculated: C 90.25, H 5.37, N 4.39; found: C90.16, H 5.41, N 4.45.

Yield: 87.5 percent of theory. Light yellow felted small needles fromdioxane-ethanol. Melting point: 166 to 166.5C.

Analysis: C H N (384.46). Calculated: C 87.47, H 5.24, N 7.29; found: C87.46, H 5.34, N 7.21.

Yield: 92.5 of theory. Pale yellow felted small needles fromtetrachlorethylene. Melting point: 242 to 242.5C.

Analysis C H N (460.55). Calculated: C 88.66, H 5.25, N 6.08; found: C88.71, H 5.32, N 5.84.

Yield: 92.0 percent of theory. Practically colorless very fine crystalsfrom tetrachlorethylene. Melting point: 218 to 219C.

mQQ

Yield: 97.7 percent of theory. Pale yellow glistening small crystalsfrom o-dichlorobenzene. Melting point: 300 to 301C Analysis: C ,,H N(460.55). Calculated: C 88.66, H 5.25,N6.08;found:C88.73,H5.31,N5.93.

EXAMPLE 12 10.31 g of 3-[4'-methyl-phenyl-(1)]-5,6diphenyll,2,4-triazineof formula benzalaniline and 16.7 g of potassium hydroxide powdercontaining about 10 percent of water are stirred into 200 ml ofdimethylformamide with exclusion of air, during which a yellowish browncoloration gradually develops. The temperature is raised to 60C over thecourse of 30 minutes, and the mixture stirred for a further 30 minutesat this temperature and then Analysis: C H N (384.46). Calculated: C87.47, H g

5.24, N 7.29; found: C 87.52, H 5.33, N 7.54

cooled to room temperature. Now ml of water and 200 ml of 10 percentstrength hydrochloric acid are successively added dropwise. Theprecipitated reaction product is washed with a great deal of water andwith 500 ml of methanol and is dried. About 9.5 g, corresponding to 69.2percent of theory, of 3-[stilbenyl-(4 ')]5,6-diphenyl-1,2,4-triazine offormula j I ll are obtained in the form of a light yellow powder. Afterthree recrystallizations from dimethylformamideethanol-waterwithgt heaid of activated charcoal, light yellow very fine felted crystals ofmelting point 202.5 to 203.5C are obtained.

Analysis: C H N (411.48). Calculated: C 84.64, H 5.14, N 10.21;found: C84.60, H 5.32, N 10.24.

2. Process according to claim 1, characterized by using as the startingsubstance a compound of formula
 3. Process according to claim 1,characterized by using as the starting substance a compound of formula4. Process according to claim 1, characterized by using as the startingsubstance a compound of formula
 5. Process according to claim 1,characterized by using as the strongly basic alkali compound an alkalimetal compound of foRmula KOCm-1H2m-1 in which m denotes an integerhaving a value of not more than
 6. 6. Process according to claim 3,characterized by using as the strongly basic alkali compound an alkalimetal compound of formula KOCm-1H2m-1 in which m denotes an integerhaving a value of not more than
 6. 7. Process according to claim 3,characterized by using as the strongly basic alkali compound potassiumtert.-butylate.
 8. Process according to claim 3, characterized by usingas the strongly basic alkali compound, potassium hydroxide containing 0to 10 percent of water.
 9. Process according to claim 1, characterizedby using as the strongly basic alkali compound potassium tert.-butylate.10. Process according to claim 1, characterized by using as the stronglybasic alkali compound, potassium hydroxide containing 0 to 10 percent ofwater.
 11. Process according to claim 4, wherein R'' is biphenyl and Xis hydrogen.